Thermo-catalytic　CO　methanation　has　been　widely　investigated　as　an　attractive　strategy　for　the　removal　of　CO　in　H2-rich　stream.　In　this　paper,　UV　irradiation　was　introduced　into　the　system　of　thermo-catalytic　CO　methanation　over　a　noble-metal-free　Ni/TiO2　catalyst.　It　is　found　that　UV　irradiation　can　remarkably　promote　the　CO　conversion　and　CH4　selectivity,　as　well　as　an　excellent　catalytic　stability　under　the　thermo-catalytic　reaction　conditions.　Results　of　XPS,　FT-IR,　and　TPO　measurements　for　the　Ni/TiO2　catalyst　indicate　that　upon　UV　light　irradiation,　the　photo-generated　electrons　are　transferred　from　the　TiO2　support　to　the　adjacent　Ni　sites,　and　causes　the　Ni　sites　with　increased　surface　electron　density　which　subsequently　enhances　the　adsorption　and　activation　of　CO　molecules　at　Ni　sites,　and　ultimately　promotes　the　catalytic　performance　of　CO　methanation.　This　result　shows　that　photo-excitation　of　TiO2　can　act　as　an　electron　donor　to　promote　the　thermo-catalytic　performance　of　CO　methanation　over　Ni/TiO2.　©　2014　Elsevier　B.V.